Hydroxycarboxylic acid arylides



. 30* aniline Patented Nov. 28, 19:33

Q 1,936,926] 1 i H YDROXYCARBOXYLIC A CI D RYLI E's'f Karl Zahn, Kurt Schjmmelschmidt, and Heinrich i Koch, Frankfort-on-the Main Hochst. Germany, assignors to General AniiineaWcrks, 111C".

New York N. L, a corporation of Delaware N Drawing. 'Applicaticn February" 3,' 1932, Serial No. 590,782, and in Germany February 5' Claims. (01; 260-124) 'The"pr'esent invention relates to hydroxy- .carboxylic acid aryl'ides. 1 I

'We have found that arylides which, in the form of theiralkaline salts, possess a high aff nity for '5 vegetable fiber, are obtainable by condensing 2.3-hydroxynaphthoic f acid or a substitution 7 product with 4-,aminodiphenyl or a substitution product thereof. The term substitution prods ucts of 4-amino-diphenyl as' used herein is in- 0 tended to include compounds containing a bridge in the 2.2-position of the diphenyl nucleus, as, ior instance, Z-aminofiuorene, 2 -aminofluorenone, 2- amino carbazole, J2-amino-diphenylene-oxide or their substitution products; the term substituaminodipheny -is to besimilarly understood. The condensation may be conducted according to known general methods ior making arylides of 2.3- hydroxynaphthoic acid. 1

when dyeing with the aidvofmechanical apparatu V ing a substituted or unsubstituted phenyl-group inpara-position totheaminoagroup of the arylide -.cbmpound V the, substantivity is increased.

Whereas, for instance, 2CBEhydroxynaLphthoyhlaminobenzene is absorbed by the fiber tothe extent of 10 per cent, the arylide obtainable by introducing. a phenyl-groupin t-position of the radical, namely the 2f.-3'-hydroxynaphthoyl-4-amino-dipheny1 or" the Formula I, isabsorbed undersame conditions to the extent of-60 per cent; The 2.3 -hydr oxynapthoy1- 1-amino-2-methoxybenzene, for instance, has a 35 substantivity of 12 per cent whereas-the223% hydroxynaphthoyl 4 arnino-3-methoxydipheny1 has a substantivity ofper cent. lf'he 223- hydroxynaphthoyl l amino-2.5-dimethoxybenzene is absorbed to the extent of l7-to 18' per cent,

'4 whereas the 2.3'-hydroxynapt l 1oyl 4 amino- 2.5 -dimethoxydiphenyl is absorbed to theextent of 10 per cent. Furthermore, there are,for instance, absorbed y M 2",3f-hydroxynaphthoy1-4-amino -4' ethoxy 451 diphenyl of the Formula II to the extent of '10 per cent.

2.3-'-hydr0Xyna-phthoy1 2 aminofluorene of the Formula III to :the extent of about per cent;v i i v. 2.3'-hydroxynaphthoyl-2-aminofluorenone of theFormula IV to the extent of about 60'per cent.

- 2K3".-'hydroxynaphthoyl-2 aminocarbazole of" theFormula Vto the extent of '80 to percent. and 1 I vA high substantivity is very much desired I In general, it maybe said that by-introducl 2.3' -hydroXynaphthoy1-2-aminodiphenylenef' oxide of the Formula cent.

Most of the new arylides have a much better afiinity for the;fiber' than the naphthol'knowm to'be the most substantive, namely'the 2'.3"- hythe extent of 60 per droxynaphthoyl-Z-aminonaphtha1ene' which. is f1 absorbed by the fiber under sam the extentof 40 per cent.''; i The new arylidesare'characterizedbyithe following"generaliormulah Ji 1 J conditions ;-to

wherein Y stands for hydrogen, alkoxy or halo- "gen, X stands for hydrogen or the two X's joint 1y stand fora substituent of they group consisting y of CH2, CO, NI-I or O, and wherein the diphenylnucleus may be further substituted by alkyl, al-' koxy, halogen, the nitro-, acid-dialkyl-amino-group.

' Furthermore, we have found that am -dyestuffs of good properties are obtainable by coupling an arylide of the kind mentioned above with any diazo compound, either insubstancaon the fiber or in the presence of any of the usual substrata which are adapted for theproductionof lakes.

Whenproducing the dyestuffs on the fiber, it is advantageous to use components which do not 7 contain groups rendering the dyestuffs soluble t of the dyestuffs obtained could not be foreseen.

in water as, for instance, a sulfonic acid or ca r-v boxylic acid group. I

Since derivatives of 4-aminodiphenyl, '2-aminofluorene, 2-aminofiuorenone, etc., hitherto, have not been used forthe preparation of dyestuffs of the said kind, the fastness properties With the aid of the azo-dyestuffs obtainable according'to this. invention there are obtained without complicated after-treatment, dyeings of great tinctorial power- The dyestuffs obtained from 2 .3 -hydroxynaphthoyl-4-amino 2 .5 -dial' koxydiphenyl, moreover, possess a good fastnessv to light. In the case of "these coupling compoa nents the fastness to light lies between grades 6 and 7 of the standards for .Fastness to Light of the Echtheitskommission der 'Fachgruppe,

fiir Chemie der Farbenund Textilindustrie im Verein Deutscher Chemiker, 4th edition, 1928 (reprinted in Schultz, Farbstofitabellen, 7th edition,vol. 1, 1931, page XXXI etseq.) r

. Manyof the dyestuffs have brilliant tints'which V are very much in demand and they are, therefore,

wherein represents an aromatic radical, Y. stands for hydrogen, alkoxy orhalogen, Xstands 5 forhydrogn' or the two Xs jointly standfor a subthe nitro-,

stituent of the group consisting of CH2, 00, NH or O, and'wherein the diphenyl nucleus may be further substituted by alkyl, alkoXy, halogen,

pherlyl or sulfonic-acid-dialkylamino-group.

' The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight:

(1) 1-88 parts of 2.3-hydroxynaphthoic acid 7 i and, 169 parts of 4-aminodiphenyl are introision parts of phosphorus trichloride are graduduced into-2000 parts of toluene; to this suspenally. added, drop by-drop, at 70 0., while stirring.

I When the 'wholequantityof phosphorus trichloric acid gas can be observed. After some hours,

ride has beeniadded, the mixture is heated to boiling whilecontinuously stirring, and boiling is continued as long as anfevolution of hydrochlothe reaction is finis'hed and the mixture is allowed :to' cool. The product which is obtained in a crystalline form is separated from the toluene ing with a yield of -per cent.- By recrystallizaphenylor sulfonic in, alcoholic alkali to a yellow solution which on becoming darker in color.

by filtering by suction and purified by boiling it with dilute sodium carbonate'solution, in which the arylide is insoluble. After drying, 270 parts of a colorless product are obtained,.corre'spondtion from benzyl alcohol the 2.3'-hydroxynaphthoyl--aminodiphenyl of melting point 283 C. is obtained in an entirely pure state. It dissolves dilution with water is de-colorized with separation of the free arylide. I

By using instead of the 4-amino-diphenyl the 4-amino-4 -ethoxydipheny1, the v2 .3 -hydroxynaphthoyll-arnino 4' ethoxydiphenyl is obtained, melting at 275 0. and likewise dissolving in alcoholic alkali to a yellow solution 7 from which, however,the arylide does not separate on dilution with water. I

In the same manner, there are obtained, the

2 .3 -hydroxynaphthoyl -4-amino 4 nitrodiphenyl, melting at 324;Cfto 325C; I

I 2 .3 -hydroxynaphthoyl 4-amino 4 chloro diphenyl, meltingat 304 C. 130-306" 0;,

6' -bromo2 .3 hydroxynaphthoyl i aminodi 7 phenyl, melting at 322 C. to 323 0;,

. 7 -methoxy-2.3-hydroxynaphthoyl l amiho diphenyl, melting at 302 C. to 303 0.,

i 2' .3 hydroxynaphthoyl 4-amino 3 methoxydiphenyl, melting at 214 C. to 216 0., i 2' .3 hydroxynaphthoyle l-amino 2.5 dimethoxydiphenyl, melting at 219 C. to 220 0., 6' -:bromo 2.3' -hydroxynaphthoyle i-amino- 2.5-dime'thoxydiphenyl, melting at 233 V0. to

' '2 .3 hydroxynaphthoyl- 4 amino 2.5.4 -tri methoxydiphenyl, melting at 221 0. to 224 0.,

' 2 .3 -hydroxynaphthoyl -4-amino-2'.5-dimeth; oxyi' -phenyhdiphenyl, melting at 221 0. to 222 0.,

oxy-diphenyl, melting at 214 0.,

' oxy-diphenyl, melting at295 C."to 296 0.,

2 .3 -hydroxynaphthoyl-4-amino-2 -n itro-di' phenyl, melting at 264'0."to 266 0., 2".3" hydroxynaphthoyl 4 amino dipheny 4'-sulfonic acid-dimethylamide, melting at 263 2 .3 hydroxynaphthoyl 4 aminodiphenyl 1 4'-sulfonic acid-diethylamide, melting at 263 '0. to 264 0., J v

2-.3' hydroxynaphthoyl-i-ainino 3 chlordi-I phenyl, melting at 257 C. to 258 0.,

2f .3 hydroxynaphthoyl l-amino 3 methyldiphenyLmelting at 239 ,0, 1 j V '(2)' 188 parts of 2.3-hydroxyhaphthoic acid and'l81' parts of 2 -aminofluorene are introduced while stirring into 2500parts of chlorobenzene and 70 parts of phosphorustrichloride are gradually 80 C. Thereupon, the mixture is heated'to boiling while continuously stirring, and heating is continued until the evolution of hydrochloric acid f gas has ceased. After some' hours, the reaction is complete and the mixture is allowed to cool. 140.

The crystalline product is separated from the chlorobenzene byyfiltering by suction and purified by boiling it'with' dilute sodium carbonate solution,in'which the arylide is insoluble. After a a drying, thereare obtained 290'parts of ayellowish product which melts vat 279 0. t0"28,0 0., whilst The 2".3.-hydr oxynaphthoxyl-2aminofiuorene' dissolves in alco holic alkali to a yellow solution with anintense greenfiuorescence, from which on. dilution with water the arylide again separates owing to hytion of 40 per cent. strength whereby the whole dissolves to a red solution. The solution is fil-- tered, run into dilute hydrochloric acid and the precipitate formed thereby is filtered by suction and dried. There is obtained the 2.3'.-hydroxy-' naphthoyl-Z-aminofiuorenone of melting point 295 C. to 298 C. i

(4) A suspension in 3500 parts of anhydrous xylene, of 217 parts of 2-aminocarbazole and 235 parts of 2.3-hydroxynaphthoic acid of 96 per cent. strength is heated to boiling; a solution of 75 parts of phosphorus trichloride in 100 parts of xylene is then added drop by drop within one hour while stirring, and the .whole is heated in a reflux apparatus until the evolution of hydrochloric acid is complete. The whole is allowed to cool to about C., the 2'.3 -hydroxynaphthoyl-Z-aminocarbazole which has separated is filtered by suction and washed with xylene hav-' ing a temperature of 90 C. the adherent-xylene is removed by treatment with steam and any unchanged 2.3-hydroxynaphthoic acid which may be present, is eliminated by extraction with sodium carbonate solution. The product is again filtered by suction and dried. 380 parts of 2'.3-hydroxynaphthoyl-Z-aminocarbazole are obtained. In an analogous manner, there is obtained from 2.3-hydroxynaphtholic acid and 2-aminodiphenylene-oxide the 2.3'-hydr'oXynaphthoyl-2- aminodiphenylene-oxide of melting point- 300 C., which dissolves in alcoholic alkali to a yellow solution. By pouring this solution into water, the arylide hydrolizes and precipitates completely. We claim: 7 1. The compounds of the following general formula:

' compounds soluble in high-boiling organic solaffinity for the Vegetable fiber.

koxy, halogen, the nitro-, phenylor sulfonic aciddialkyl-a nino-group, being crystallized" compounds soluble in high-boiling organic solvents and in alcoholic alkali'and possessing a high afiinity for the vegetable fiber.

2. The compounds of the following 7 general formula:

wherein Y'stands for hydrogen, alkoxy or halogen, and the diphenyl nucleus may be substituted by alkyl, alkoxy, halogen, the nitro-, phenylor sulfonic acid-dialkyl-amino-group, being crystallized compounds soluble in high-boiling organic sol-,

vents and with a yellow color in alcoholicalkali and possessing a high affinity for the vegetable fiber. L. l y 3., The compound of the following formula 'EQ being a crystallized compound, melting at 21 9? C- to 220 C., soluble in high-boiling organicsolvents and with a yellow color in alcoholic alkali and possessing a high affinity for'the vegetable fiber.

4. The compound of the followingi'ormula:

. v H 115 being a crystallized compound, melting at 283 C., 1

soluble in high-boiling organic solvents and with a yellowcolor in alcoholic alkaliand possessing a high aflinity for'the vegetable fiber. a

Y 5. The compounds ,of the following genera formula: I r

wherein X stands for a substituent offthegroup' consisting of CH2, CO, NH or 0, being crystallized vents and in alcoholic alkali and possessing a high 'KARLZAI-IN. I l KURT SCHIMMELSCHMIDT. HEINRICH KOCH.

DISCLAIMER 1,936,926.Karl Zahn, Kurt Schimmelschmidt, and Heinrich Koch, of Frankforton-the-Main-Hochst, Germany. HYDROXYCARBOXYLIC ACID ARYLIDES.

Patent dated November 28, 1933. Disclaimer filed April 16, 1936, by the assignee, General Aniline Works, Inc.

Hereby enters this disclaimer to claims 1, 2, 3, and 4.

[Ofiicial Gazette lllay 12, 1.936.] 

